Acostajama5053

70 mA h g-1 (M = Cr) and 362.46 mA h g-1 (M = Mo) and the OCVs can approach 0.034 V (M = Cr) and 0.042 V (M = Mo). Therefore, Cr2TiC2O2 and Mo2TiC2O2 are expected to be promising anode materials for SIBs due to their excellent properties, such as good electronic conductivity, low sodium diffusion barrier, and high theoretical sodium storage capacity.This study is the first report on liquid water and ice imaging conducted at a pulsed spallation neutron source facility. Neutron imaging can be utilised to visualise the water distribution inside polymer electrolyte fuel cells (PEFCs). Particularly, energy-resolved neutron imaging is a methodology capable of distinguishing between liquid water and ice, and is effective for investigating ice formation in PEFCs operating in a subfreezing environment. The distinction principle is based on the fact that the cross sections of liquid water and ice differ from each other at low neutron energies. In order to quantitatively observe transient freezing and thawing phenomena in a multiphase mixture (gas/liquid/solid) within real PEFCs with high spatial resolution, a pulsed neutron beam with both high intensity and wide energy range is most appropriate. In the validation study of the present work, we used water sealed in narrow capillary tubes to simulate the flow channels of a PEFC, and a pulsed neutron beam was applied to distinguish ice, liquid water and super-cooled water, and to clarify freezing and thawing phenomena of the water within the capillary tubes. Moreover, we have enabled the observation of liquid water/ice distributions in a large field of view (300 mm × 300 mm) by manufacturing a sub-zero environment chamber that can be cooled down to -30 °C, as a step towards in situ visualisation of full-size fuel cells.The geometric configuration of olefin products is often driven by thermodynamic control in synthesis. Methods enabling switching of cis/trans selectivity are rare. Recently, photosensitized approaches have emerged as a powerful tool for accomplishing this task. In this report, we report an in situ isomerization of an N-heterocyclic carbene (NHC)-bound intermediate by a photo-induced energy transfer process that leads to selective access of chiral allylic fluorides with a cis-olefin geometry. In the absence of a photocatalyst or light, the reaction proceeds smoothly to give (E)-olefin products, while the (Z)-isomer can be obtained under photosensitizing conditions. Preliminary mechanistic experiments suggest that an energy transfer process might be operative.Air quality in cities is influenced not only by emissions and chemical transformations but also by the physical state of the atmosphere which varies both temporally and spatially. Increasingly, tall buildings (TB) are common features of the urban landscape, yet their impact on urban air flow and dispersion is not well understood, and their effects are not appropriately captured in parameterisation schemes. Here, hardware models of areas within two global mega-cities (London and Beijing) are used to analyse the impact of TB on flow and transport in isolated and cluster settings. Results show that TB generate strong updrafts and downdrafts that affect street-level flow fields. Velocity differences do not decay monotonically with distance from the TB, especially in the near-wake region where the flow is characterised by recirculating winds and jets. Lateral distance from an isolated TB centreline is crucial, and flow is still strongly impacted at longitudinal distances of several TB heights. Evaluation of a wakeed layer height (MLH) empirical model with parameters derived from a third mega-city (London). The MLH model works well in central Beijing but less well in suburban Paris. The variability of the physical meteorology across different vertical scales discussed in this paper provides additional context for interpreting air quality observations.The effects of antiaromaticity and destructive quantum interference (DQI) are investigated on the charge transport through dibenzo-[a,e]pentalene (DBP). 5,10-Connectivity gives high single-molecule conductance whereas 2,7 gives low conductance due to DQI. Comparison of the 5,10-DBP with phenyl and anthracene analogues yields the trend GDBP ≈ GAnth > GPh, despite the aromatic anthracene having a larger HOMO-LUMO gap than 5,10-DBP. This is explained by unfavourable level alignment for 5,10-DBP.Organic semiconductors including conjugated polymers and small molecules can be applied in many fields due to their unique advantages, such as light weight, solution processability, easy functionalization etc. During the past ten years, we mainly focused on the design and synthesis of conjugated polymer donor materials and small molecular acceptor materials for organic solar cells and hole transport materials for perovskite solar cells. To obtain planar conjugated polymers, low cost small molecular acceptors, and dopant-free hole transport polymers, we adopted intramolecular noncovalent interactions (INCIs) as the design strategy. In this brief review, we will demonstrate that the INCI strategy is very efficient in the design of high performance photovoltaic materials.The azepinoindole framework present in natural alkaloids such as subincanadine F, ibogaine and catharanthine was formed in a novel acid-promoted cyclization-rearrangement of tryptamine-derived N-sulfonyl enamines. The latter were conveniently prepared via a cesium carbonate mediated formal vinylic substitution reaction of 2-bromoallyl sulfones (allenyl sulfone surrogate) and tryptamine sulfonamides. The azepinoindole forming cyclization-rearrangement involves the initial generation of a six-membered tetrahydro-β-carboline derivative. TP-0903 nmr The steric bulk of the N-sulfonyl group on tryptamine plays an important role in deciding the reaction outcome.Computational studies were performed on non-classical thieno[3,4-c][1,2,5] thiadiazole and its pi donor derivatives (TT dyes) so as to delineate the factors responsible for their near-infrared (NIR) absorption. For all dyes except the unsubstituted bare dye, adiabatic singlet-triplet energy gaps (estimated through the ΔSCF procedure using the B3LYP and M062X DFT methods and SFTDDFT with the 5050 functional) were less than 1eV. Percentage calculations of the biradicaloid character suggested a moderate biradicaloid nature in all derivatives. There was a resemblance between the frontier molecular orbital (MO) picture of the TT bicyclic ring and the degenerate non-bonding molecular orbitals of Trimethyleneethane (TME, a known biradical). Inter-fragment charge transfer analysis revealed not only a considerable donation of charge to the central ring (Acceptor, TT part) but also substantial charge redistribution within the ring itself. From these results, it was inferred that NIR absorption, in these dyes, was due to (1) a reduced HOMO-LUMO gap (HLG) as a TME biradical substructure forms its chromophoric part; and (2) charge transfer from the donor substituents. The non-bonding nature of the S atom, in the bare dye, with its neighbouring N/C atom (of the highest occupied π-MOs), led to an examination of its electronic structure using the ab initio valence bond method. The relatively large weight and energetic stability of the biradicaloid VB structures compared to those of the ylidic structures clearly disclosed the importance of biradicaloid structures in the overall resonance of the bare dye. Their utility as singlet fission materials was screened using singlet and triplet energy-based molecular structure activity criteria. The results were encouraging, demanding experiments to reaffirm the materials' usefulness.We have developed an amphiphilic pH probe (P1CS) to detect pH levels in the plasma membrane in cancer cells. An elevated fluorescence signal at 550 nm at the cell surface of cancer cells (MDA-MB-231, HeLa cells) prompted the application of P1CS as a pH marker for the cancer cell surface, discriminating it from normal cells (WI-38). link2 Moreover, the probe enables labeling of the surface of multilayered tumor spheroids, which promotes its use as a marker for the surface of tumor tissue.Primer design and condition optimization for PCR are tedious and labour-intensive. To conveniently achieve high selectivity, sensitivity and robustness, herein, we first report a new strategy with Se-dNTPs to enhance PCR specificity (over 240-fold) and sensitivity (up to single-digit), effectively eliminating non-specific products and simplifing PCR design and optimization.Isocyanates are the key intermediates for several organic transformations towards the synthesis of diverse pharmaceutical targets. Herein, we report the development of an oxidant-free protocol for electrochemical in situ generation of isocyanates. This strategy highlights expedient access to benzimidazolones and quinazolinones and eliminates the need for exogenous oxidants. link3 Furthermore, detailed mechanistic studies provide strong support towards our hypothesis of in situ isocyanate generation.Myoglobin (Mb) is considered as the optimal system for capturing molecular oxygen (O2) in aqueous solution under natural conditions. Therefore, the preparation of artificial systems that mimic the function of Mb is a long-standing and challenging objective. Various sophisticated iron porphyrins have been designed and synthesized to realize O2 biding at their axial positions. Although all of these compounds reversibly bind O2 in absolute organic solvents, no stable O2 adducts were obtained in aqueous solution. The reason for this is the immediate autoxidation of O2 adducts by water molecules. To achieve O2 binding in aqueous solution, the iron center of the porphyrin must be placed in a hydrophobic environment, wherefrom a water molecule is strictly excluded. Another essential requirement for a Mb model is the preparation of an electron-donative axial ligand that plays the role of proximal histidine (His). As an artificial O2 receptor that satisfies these challenging requirements, a supramolecule termed "hemoCD1" has been constructed. HemoCD1, a 1  1 inclusion complex of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphinatoiron(ii) (FeIITPPS) with a per-O-methylated β-cyclodextrin dimer bearing a pyridine linker (Py3CD), reversibly binds O2 in aqueous solution at neutral pH and ambient temperature. The electronic spectra as well as the functions of hemoCD1 are analogous to those of Mb or its tetramer, hemoglobin (Hb). This is the first example of an artificial Hb/Mb biomimetic model capable of function in aqueous solution. Such a study on hemoCD1 as a Hb/Mb model has expanded research objectives to (1) syntheses of hemoCD1 analogues having distinct characteristics, (2) modeling enzymatic reactions of peroxidase, heme oxygenase, and cytochrome c oxidase in water, (3) development of fully synthetic artificial oxygen carriers (AOCs) utilized in animal blood, and (4) selective binding and removal of toxic small molecules, such as carbon monoxide (CO) and cyanide (CN-) in living organisms.The decoration of Cu2O nanoparticles with guanosine-rich aptamers can significantly enhance their peroxidase activity at neutral pH and endow them with specific recognition capabilities. Both the phosphate backbone and guanine of the aptamers contribute to the enhancement. The excellent enzyme-like properties of this Cu2O-aptamer system make it a versatile platform for the development of neutral pH biosensors.